Apparatus and methods for performing an in-situ etch of reaction chambers with fluorine-based radicals

ABSTRACT

An apparatus and method for cleaning or etching a molybdenum film or a molybdenum nitride film from an interior of a reaction chamber in a reaction system are disclosed. A remote plasma unit is utilized to activate a halide precursor mixed with an inert gas source to form a radical gas. The radical gas reacts with the molybdenum film or the molybdenum nitride film to form a by-product that is removed from the interior of the reaction chamber by a purge gas.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Nonprovisional of, and claims priority to and thebenefit of, U.S. Provisional Patent Application No. 63/021,514, filedMay 7, 2020 and entitled “APPARATUS AND METHODS FOR PERFORMING ANIN-SITU ETCH OF REACTION CHAMBERS WITH FLUORINE-BASED RADICALS,” whichis hereby incorporated by reference herein.

FIELD OF INVENTION

The present disclosure relates generally to an apparatus and methods forcleaning a reaction chamber after a film has been deposited on interiorwalls of the reaction chamber. The present disclosure more specificallyrelates to using halogen-based radicals for performing the cleaning oran in-situ etch of the deposited film.

BACKGROUND OF THE DISCLOSURE

Semiconductor fabrication processes for forming semiconductor devicestructures, such as, for example, transistors, memory elements, andintegrated circuits, are wide ranging and may include depositionprocesses. The deposition processes may result in films such asmolybdenum or molybdenum nitride deposited on the substrates.

During the deposition processes, the molybdenum or molybdenum nitridefilms may also accumulate on interior walls of the reaction chamber. Iftoo much of these films accumulate on the walls, adverse effects mayoccur such as drifting process performance due to temperatureirregularities caused by the accumulated films. In addition, theaccumulated films may cause particle issues on processed substrates.

Traditional preventative reaction chamber maintenance may need periodicreplacement of parts for the reaction chamber. This may result insignificant down time (on the order of 1 week or more), causing a highloss in production.

Accordingly, apparatuses and methods are desired to clean depositedmolybdenum or molybdenum nitride films from walls of reaction chambersthat do not require a significant down time in production.

SUMMARY OF THE DISCLOSURE

This summary is provided to introduce a selection of concepts in asimplified form. These concepts are described in further detail in thedetailed description of example embodiments of the disclosure below.This summary is not intended to identify key features or essentialfeatures of the claimed subject matter, nor is it intended to be used tolimit the scope of the claimed subject matter.

In at least one embodiment of the invention, a method for cleaning aninterior wall of a reaction chamber is disclosed. The method comprises:providing a reaction chamber in which a molybdenum film is deposited onan interior wall of the reaction chamber; igniting a remote plasma unitby flowing an inert gas into the remote plasma unit; flowing a halideprecursor into the remote plasma unit to form a radical gas; flowing theradical gas from the remote plasma unit into the reaction chamber,wherein the radical gas reacts with the molybdenum film; and flowing apurge gas to remove a by-product of the reaction of the radical gas withthe molybdenum film from the reaction chamber; wherein the molybdenumfilm comprises at least one of: molybdenum; or molybdenum nitride.

In at least one embodiment of the invention, a reaction system fordepositing a semiconductor film is disclosed. The reaction systemcomprises: a reaction chamber configured to hold a substrate to beprocessed, the reaction chamber having a deposited film on an interiorof the reaction chamber, wherein the deposited film comprises at leastone of: molybdenum or molybdenum nitride; a remote plasma unit; a halideprecursor source configured to provide a halide gas to the remote plasmaunit; an inert gas source configured to provide an inert gas to theremote plasma unit; a first reactant precursor source configured toprovide a first reactant precursor to the reaction chamber, wherein thefirst reactant precursor does not enter the remote plasma unit; and asecond reactant precursor or purge gas source configured to provide asecond reactant precursor or a purge gas to the reaction chamber;wherein the remote plasma unit is configured to activate a mixture ofthe halide gas and the inert gas to form a radical gas that flows to thereaction chamber; and wherein the radical gas reacts with the depositedfilm to remove the deposited film from the reaction chamber.

In at least one embodiment of the invention, a batch reaction system fordepositing a semiconductor film is disclosed. The reaction systemcomprises: a reaction tube configured to hold a substrate boat to beprocessed, the reaction tube having a deposited film on an interior ofthe reaction tube, wherein the deposited film comprises at least one of:molybdenum or molybdenum nitride; an in situ radical generator; a halideprecursor source configured to provide a halide gas to the reactiontube; an inert gas source configured to provide an inert gas to thereaction tube; an oxygen gas source configured to provide an oxygen gasto the reaction tube; a first reactant precursor source configured toprovide a first reactant precursor to the reaction tube; and a secondreactant precursor source configured to provide a second reactantprecursor to the reaction chamber; wherein the in situ radical generatoris configured to activate the halide gas to form a radical gas in thereaction tube; and wherein the radical gas reacts with the depositedfilm to remove the deposited film from the reaction tube.

For purposes of summarizing the invention and the advantages achievedover the prior art, certain objects and advantages of the invention havebeen described herein above. Of course, it is to be understood that notnecessarily all such objects or advantages may be achieved in accordancewith any particular embodiment of the invention. Thus, for example,those skilled in the art will recognize that the invention may beembodied or carried out in a manner that achieves or optimizes oneadvantage or group of advantages as taught or suggested herein withoutnecessarily achieving other objects or advantages as may be taught orsuggested herein.

All of these embodiments are intended to be within the scope of theinvention herein disclosed. These and other embodiments will becomereadily apparent to those skilled in the art from the following detaileddescription of certain embodiments having reference to the attachedfigures, the invention not being limited to any particular embodiment(s)disclosed.

BRIEF DESCRIPTION OF THE DRAWING FIGURES

While the specification concludes with claims particularly pointing outand distinctly claiming what are regarded as embodiments of theinvention, the advantages of embodiments of the disclosure may be morereadily ascertained from the description of certain examples of theembodiments of the disclosure when read in conjunction with theaccompanying drawings, in which:

FIG. 1 illustrates a non-limiting exemplary process flow, demonstratinga method for cleaning a molybdenum or molybdenum nitride film frominterior walls of a reaction chamber according to the embodiments of thedisclosure.

FIG. 2 illustrates a cross-sectional schematic diagram of a filmdeposition system according to the embodiments of the disclosure.

FIG. 3 illustrates a batch reactor system in accordance with at leastone embodiment of the disclosure.

The illustrations presented herein are not meant to be actual views ofany particular material, structure, or device, but are merely idealizedrepresentations that are used to describe embodiments of the disclosure.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

Although certain embodiments and examples are disclosed below, it willbe understood by those in the art that the invention extends beyond thespecifically disclosed embodiments and/or uses of the invention andobvious modifications and equivalents thereof. Thus, it is intended thatthe scope of the invention disclosed should not be limited by theparticular disclosed embodiments described below.

As used herein, the term “substrate” may refer to any underlyingmaterial or materials that may be used, or upon which, a device, acircuit, or a film may be formed.

As used herein, the term “cyclical chemical vapor deposition” may referto any process wherein a substrate is sequentially exposed to one ormore volatile precursors, which react and/or decompose on a substrate toproduce a desired deposition.

As used herein, the term “atomic layer deposition” (ALD) may refer to avapor deposition process in which deposition cycles, preferably aplurality of consecutive deposition cycles, are conducted in a reactionchamber. Typically, during each cycle the precursor is chemisorbed to adeposition surface (e.g., a substrate surface or a previously depositedunderlying surface such as material from a previous ALD cycle), forminga monolayer or sub-monolayer that does not readily react with additionalprecursor (i.e., a self-limiting reaction). Thereafter, if necessary, areactant (e.g., another precursor or reaction gas) may subsequently beintroduced into the process chamber for use in converting thechemisorbed precursor to the desired material on the deposition surface.Typically, this reactant is capable of further reaction with theprecursor. Further, purging steps may also be utilized during each cycleto remove excess precursor from the process chamber and/or remove excessreactant and/or reaction byproducts from the process chamber afterconversion of the chemisorbed precursor. Further, the term “atomic layerdeposition,” as used herein, is also meant to include processesdesignated by related terms such as, “chemical vapor atomic layerdeposition”, “atomic layer epitaxy” (ALE), molecular beam epitaxy (MBE),gas source MBE, or organometallic MBE, and chemical beam epitaxy whenperformed with alternating pulses of precursor composition(s), reactivegas, and purge (e.g., inert carrier) gas.

As used herein, the term “film” and “thin film” may refer to anycontinuous or non-continuous structures and material formed by themethods disclosed herein. For example, “film” and “thin film” couldinclude 2D materials, nanolaminates, nanorods, nanotubes, ornanoparticles, or even partial or full molecular layers, or partial orfull atomic layers or clusters of atoms and/or molecules. “Film” and“thin film” may comprise material or a layer with pinholes, but still beat least partially continuous.

A number of example materials are given throughout the embodiments ofthe current disclosure, it should be noted that the chemical formulasgiven for each of the materials should not be construed as limiting andthat the non-limiting example materials given should not be limited by agiven example stoichiometry.

The present disclosure includes an apparatus and method for cleaning areaction system that performs a molybdenum film deposition process.Molybdenum thin films may be utilized in a number of applications, suchas, for example, low electrical resistivity gap-fill, liner layers for3D-NAND, DRAM word-line features, metal gate, DRAM top electrode,memory, or as an interconnect material in CMOS logic applications.

FIG. 1 illustrates a method 100 for cleaning a reaction system inaccordance with at least one embodiment of the invention. The method 100comprises: (1) providing a reaction chamber that has a depositedmolybdenum film 110; (2) igniting a remote plasma unit 120; (3) flowinga halide precursor into the remote plasma unit 130; (4) flowing aradical gas formed in the remote plasma unit into the reaction chamber140; and (5) purging by-products from the reaction chamber 150. Theprocess then may exit in a step 160, whereby further processing stepsoccur, such as additional film deposition processes, cleaning processes,or annealing processes.

The deposited molybdenum film in step 110 may comprise molybdenum ormolybdenum nitride. The igniting step 120 may comprise flowing an inertgas in to the remote plasma unit. The inert gas may comprise at leastone of: argon; xenon; or another inert gas. The remote plasma unitemployed may include one manufactured by MKS Instruments, Inc. orLightwind Corporation.

Once the plasma is ignited, the flowing the halide precursor into theremote plasma unit step 130 occurs. The halide precursor may comprise atleast one of: nitrogen trifluoride (NF₃); sulfur hexafluoride (SF₆);carbon tetrafluoride (CF₄); fluoroform (CHF₃); octafluorocyclobutane(C₄F₈); chlorine trifluoride (ClF₃); fluorine (F₂); or a combination ofthe above. This causes a formation of radical gases, comprising fluorineradicals, for example.

The formed radical gas is then flowed from the remote plasma unit intothe reaction chamber in step 140. The reaction chamber may be maintainedat temperatures ranging between 300° C. and 550° C., between 350° C. and500° C., or between 400° C. and 450° C. Temperatures that are too highmay result in an excessively reactive radical gas, causing removal ofmore than the molybdenum or molybdenum nitride films than desired.

A flow rate of the formed radical gas may affect a rate at which theremoval of the molybdenum or molybdenum nitride film occurs. The flowrate may be affected by a flow rate of the inert gas provided to theremote plasma unit. A higher flow rate of the formed radical gas mayallow for quicker removal of the film. This may reduce the downtime ofthe reaction chamber for maintenance. A higher flow rate of the formedradical gas may range between 1500 and 3000 sccm, between 2000 and 3000sccm, or between 2500 to 3000 sccm.

However, there may be situations where a lower flow rate of the formedradical gas is desired. The lower flow rate may be desired for areas ofthe reaction chamber that are more difficult for the radical gas toreach. A lower flow rate will increase a residence time of the formedradical gas, allowing it to get to the harder-to-reach areas, such asthe corners of the reaction chamber. This way, a thorough cleaning ofthe reaction chamber may be achievable. A lower flow rate of the formedradical gas may range between 50 to 500 sccm, between 100 to 300 sccm,or between 100 to 200 sccm.

The method 100 also comprises a step 150 for purging by-products fromthe reaction chamber. The radical gas reacts with the depositedmolybdenum films and may form a gaseous by-product. These by-productsare then removed from the reaction chamber by purging an inert gas. Theinert gas may comprise at least one of: argon; xenon; nitrogen; orhelium.

In at least one embodiment of the invention, fluorine radicals may beutilized to remove a molybdenum film deposited on an inner wall of thereaction chamber. The fluorine radicals are formed according to a firstreaction in the remote plasma unit during step 130, utilizing nitrogentrifluoride (NF₃) as an exemplary halide precursor:

NF₃→F*+NF₂+NF

The fluorine radicals then react with the molybdenum film in this mannerto form the by-products during step 140:

F*+Mo→MoF_(6(g))

These by-products are then removed from the reaction chamber with theinert gas in step 150.

Reactors or reaction chambers suitable for performing the embodiments ofthe disclosure may include ALD reactors, as well as CVD reactors,configured to provide the precursors. According to some embodiments, ashowerhead reactor may be used. According to some embodiments,single-wafer, cross-flow, batch, minibatch, or spatial ALD reactors maybe used.

In some embodiments of the disclosure, a batch reactor may be used. Insome embodiments, a vertical batch reactor may be used. In otherembodiments, a batch reactor comprises a minibatch reactor configured toaccommodate 10 or fewer wafers, 8 or fewer wafers, 6 or fewer wafers, 4or fewer wafers, or 2 or fewer wafers.

FIG. 2 illustrates a reaction system 200 in accordance with at least oneembodiment of the invention. The reaction system 200 may comprise: areaction chamber 210; a remote plasma unit 220; a first reactantprecursor source 230; an inert gas source 240; a halide precursor source250; a second reactant precursor or purge gas source 260; an optionalthird reactant precursor source 270; a series of gas lines 280A-280E;and a main gas line 290.

The reaction chamber 210 may have a shape and constitution depending onthe type of reaction system 200 employed, whether it be a batch,single-wafer, or mini-batch tool, for example. The shape andconstitution of the reaction chamber 210 may also depend on a processemployed in the reaction system 200; for example, whether the process isan ALD or a CVD process.

The remote plasma unit 220 is ignited by an inert gas provided from theinert gas source 240 via the gas line 280A. The remote plasma unit 220then activates a halide gas provided by the halide precursor source 250via the gas line 280B. The halide gas from the halide precursor source250 may comprise at least one of: nitrogen trifluoride (NF₃); sulfurhexafluoride (SF₆); carbon tetrafluoride (CF₄); fluoroform (CHF₃);octafluorocyclobutane (C₄F₈); chlorine trifluoride (ClF₃); fluorine(F₂); or a mixture of the above.

The activated halide gas and the inert gas form a radical gas that thentravels to the reaction chamber 210 via the main gas line 290. The maingas line 290 may also comprise an injector system if the reaction system200 is a batch or a mini-batch system. The main gas line 290 may alsocomprise a manifold, a showerhead, or an injection flange for asingle-wafer system.

The reaction system 200 may also comprise a first reactant precursorsource 230 that provides a first reactant precursor to the reactionchamber 210 via the gas line 280C in order to deposit a molybdenum filmor a molybdenum nitride film. The first reactant precursor may compriseat least one of: a molybdenum halide precursor, such as a molybdenumchloride precursor, a molybdenum iodide precursor, or a molybdenumbromide precursor; or a molybdenum chalcogenide, such as a molybdenumoxychloride, a molybdenum oxyiodide, a molybdenum (IV) dichloridedioxide (MoO₂Cl₂) precursor, or a molybdenum oxybromide.

The reaction system 200 may also comprise a second reactant precursor ora purge gas source 260 that provides a reactant precursor or a purge gasvia the gas line 280D. If the gas source 260 provides a purge gas, thepurge gas may be utilized to remove by-products of the reaction betweenthe deposited molybdenum or molybdenum nitride film and the radical gasas above described in step 150 of the method 100. If the gas source 260provides a second reactant precursor, the second reactant precursor mayreact with the first reactant precursor from the first reactantprecursor source 230 to deposit the molybdenum film or the molybdenumnitride film.

The reaction system 200 may also comprise an optional third reactantprecursor source 270 that provides an optional third reactant to theremote plasma unit 220 via the gas line 280E. The optional thirdreactant is then activated and flows to the reaction chamber 210, whereit may react with the first reactant precursor or the second reactantprecursor to deposit the molybdenum film or the molybdenum nitride film.The optional third reactant precursor source 270 may be employed wherean activated precursor is necessary, such as in low temperaturedeposition processes.

In at least one embodiment of the disclosures, a batch reactor systemmay be cleaned of a molybdenum or molybdenum nitride film depositedinside a reaction tube. FIG. 3 illustrates a batch reactor system 300 inaccordance with at least one embodiment of the invention. The batchreactor system 300 comprises: a reaction tube 310; a boat of wafers 320;a wafer boat holder 330; an in situ radical generator 340; a halide gassource 350; an inert gas source 360; an oxygen gas source 370; a firstreactant precursor source 380; and a second reactant precursor source390.

The reaction tube 310 may comprise quartz and defines a reaction spacein which a molybdenum film or a molybdenum nitride film is deposited onwafers disposed within the boat 320. The wafer boat holder 330 holds thewafer boat 320 and moves wafers into and out of the reaction tube 310.During the cleaning process, it may be preferable that the wafer boat320 be outside of the reaction tube 310.

The in situ radical generator 340 may comprise an in situ plasmagenerator, such as an inductively coupled plasma (ICP) generator or acapacitively coupled plasma (CCP) generator. Alternatively, the in situradical generator 340 may be optional as chemistries of the halide gassource 350 may prove to be unstable and naturally form radicals; forexample, a metallic surface within the batch reactor system 300 maycause formation of radicals should it get in contact with an unstablehalide gas such as nitrogen trifluoride (NF₃) or chlorine trifluoride(ClF₃).

The halide gas source 350 may provide a halide gas to the reaction tube310 via gas line and an injector structure. The halide gas may compriseat least one of: nitrogen trifluoride (NF₃); chlorine trifluoride(ClF₃); fluorine (F₂); chlorine (Cl₂); or combinations of the above. Thehalide gas may be used to etch a layer of metallic molybdenum ormolybdenum nitride formed on the quartz of the reaction tube 310. Theflow of the halide gas may range between 10 sccm and 700 sccm, between50 sccm and 600, or between 100 and 300 sccm. The flow rate of thehalide gas should be such that damage to an interior of the batchreactor system 300 is limited when the halide gas is heated. Thetemperature within the reaction tube 310 during the clean process mayrange between 300° C. and 750° C., between 350° C. and 700° C., orbetween 400° C. and 600° C. The pressure within the reaction tube 310during the clean process may range between 0.1 and 10 Torr, between 0.5and 5 Torr, or between 1 and 3 Torr.

The inert gas source 360 may provide an inert gas to the reaction tube310 via a gas line and injector structure. The inert gas may comprise atleast one of: argon; xenon; nitrogen; or helium. The inert gas mayfunction to activate in situ plasma within the reaction tube 310, shouldthe in situ radical generator 340 comprise an in situ plasma generator.The activated in situ plasma then converts the halide gas into a radicalgas. The inert gas may also be used to purge out any by-products fromthe reaction of the radical gas with the deposited molybdenum ormolybdenum nitride films on the reaction tube 310. This process mayallow for a greater selectivity to etch or clean the molybdenum ormolybdenum nitride deposited on quartz in comparison to molybdenum ormolybdenum nitride deposited on other surfaces.

Once the clean or etch process is completed, an annealing process withoxygen gas from the oxygen gas source 370 may be used to passivate thequartz material. The oxygen gas may comprise at least one of: oxygen(O₂); water vapor (H₂O); or hydrogen peroxide (H₂O₂). By passivating thequartz of the reaction tube 310, this avoids a memory effect duringfurther molybdenum or molybdenum nitride deposition.

The first reactant precursor source 380 and the second reactantprecursor source 390 may provide a first reactant precursor and a secondreactant precursor used to deposit a molybdenum or molybdenum nitridefilm onto the wafers disposed in the wafer boat 310. The first reactantprecursor may comprise at least one of: a molybdenum halide precursor,such as a molybdenum chloride precursor, a molybdenum iodide precursor,or a molybdenum bromide precursor; or a molybdenum chalcogenide, such asa molybdenum oxychloride, a molybdenum oxyiodide, a molybdenum (IV)dichloride dioxide (MoO₂Cl₂) precursor, or a molybdenum oxybromide.

The example embodiments of the disclosure described above do not limitthe scope of the invention, since these embodiments are merely examplesof the embodiments of the invention, which is defined by the appendedclaims and their legal equivalents. Any equivalent embodiments areintended to be within the scope of this invention. Indeed, variousmodifications of the disclosure, in addition to those shown anddescribed herein, such as alternative useful combination of the elementsdescribed, may become apparent to those skilled in the art from thedescription. Such modifications and embodiments are also intended tofall within the scope of the appended claims.

What is claimed is:
 1. A method for cleaning an interior wall of areaction chamber, the method comprising: providing a reaction chamber inwhich a molybdenum film is deposited on an interior wall of the reactionchamber; igniting a remote plasma unit by flowing an inert gas into theremote plasma unit; flowing a halide precursor into the remote plasmaunit to form a radical gas; flowing the radical gas from the remoteplasma unit into the reaction chamber, wherein the radical gas reactswith the molybdenum film; and flowing a purge gas to remove a by-productof the reaction of the radical gas with the molybdenum film from thereaction chamber; wherein the molybdenum film comprises at least one of:molybdenum; or molybdenum nitride.
 2. The method of claim 1, wherein thereaction chamber is integral to at least one of: an atomic layerdeposition (ALD) reaction system; a chemical vapor deposition (CVD)reaction system; a single-wafer deposition system; a batch waferdeposition system; a vertical furnace deposition system; a cross-flowdeposition system; a minibatch deposition system; or a spatial ALDdeposition system.
 3. The method of claim 1, wherein the inert gascomprises at least one of: argon; xenon; helium; or nitrogen.
 4. Themethod of claim 1, wherein the halide precursor comprises at least oneof: nitrogen trifluoride (NF₃); sulfur hexafluoride (SF₆); carbontetrafluoride (CF₄); fluoroform (CHF₃); octafluorocyclobutane (C₄F₈);chlorine trifluoride (ClF₃); fluorine (F₂); or a mixture of the above.5. The method of claim 1, wherein the purge gas comprises at least oneof: nitrogen (N₂); helium (He); argon; or xenon.
 6. The method of claim1, further comprising flowing a first reactant from a first reactantprecursor source to deposit the molybdenum film.
 7. The method of claim6, wherein the first reactant comprises at least one of: a molybdenumhalide precursor; a molybdenum chloride precursor; a molybdenum iodideprecursor; a molybdenum bromide precursor; a molybdenum chalcogenide; amolybdenum oxychloride; a molybdenum oxyiodide; a molybdenum (IV)dichloride dioxide (MoO₂Cl₂) precursor; or a molybdenum oxybromide. 8.The method of claim 6, further comprising flowing a second reactant froma second reactant precursor source to deposit the molybdenum film. 9.The method of claim 1, wherein a temperature of the reaction chamberranges between 300° C. and 550° C., between 350° C. and 500° C., orbetween 400° C. and 450° C.
 10. The method of claim 1, wherein flowingthe radical gas has a high flow mode, achieved by flowing the radicalgas at a flowrate ranging between 1500 and 3000 sccm, between 2000 and3000 sccm, or between 2500 to 3000 sccm.
 11. The method of claim 1,wherein flowing the radical gas has a low flow mode, achieved by flowingthe radical gas at a flowrate ranging between 50 to 500 sccm, between100 to 300 sccm, or between 100 to 200 sccm.
 12. A reaction system fordepositing a semiconductor film, the reaction system comprising: areaction chamber configured to hold a substrate to be processed, thereaction chamber having a deposited film on an interior of the reactionchamber, wherein the deposited film comprises at least one of:molybdenum or molybdenum nitride; a remote plasma unit; a halideprecursor source configured to provide a halide gas to the remote plasmaunit; an inert gas source configured to provide an inert gas to theremote plasma unit; a first reactant precursor source configured toprovide a first reactant precursor to the reaction chamber, wherein thefirst reactant precursor does not enter the remote plasma unit; and asecond reactant precursor or purge gas source configured to provide asecond reactant precursor or a purge gas to the reaction chamber;wherein the remote plasma unit is configured to activate a mixture ofthe halide gas and the inert gas to form a radical gas that flows to thereaction chamber; and wherein the radical gas reacts with the depositedfilm to remove the deposited film from the reaction chamber.
 13. Thereaction system of claim 14, wherein the reaction system comprises atleast one of: an atomic layer deposition (ALD) reaction system; achemical vapor deposition (CVD) reaction system; a single-waferdeposition system; a cross-flow deposition system; or a minibatchdeposition system; a spatial ALD deposition system.
 14. The reactionsystem of claim 14, wherein the inert gas comprises at least one of:argon; xenon; helium; or nitrogen.
 15. The reaction system of claim 14,wherein the halide precursor comprises at least one of: nitrogentrifluoride (NF₃); sulfur hexafluoride (SF₆); carbon tetrafluoride(CF₄); fluoroform (CHF₃); octafluorocyclobutane (C₄F₈); chlorinetrifluoride (ClF₃); fluorine (F₂); or a mixture of the above.
 16. Thereaction system of claim 14, wherein the first reactant precursorcomprises at least one of: a molybdenum halide precursor; a molybdenumchloride precursor; a molybdenum iodide precursor; a molybdenum bromideprecursor; a molybdenum chalcogenide; a molybdenum oxychloride; amolybdenum oxyiodide; a molybdenum (IV) dichloride dioxide (MoO₂Cl₂)precursor; or a molybdenum oxybromide.
 17. The reaction system of claim14, wherein flowing the radical gas has a high flow mode, achieved byflowing the radical gas at a flowrate ranging between 1500 and 3000sccm, between 2000 and 3000 sccm, or between 2500 to 3000 sccm.
 18. Thereaction system of claim 14, wherein flowing the radical gas has a lowflow mode, achieved by flowing the radical gas at a flowrate rangingbetween 50 to 500 sccm, between 100 to 300 sccm, or between 100 to 200sccm.
 19. A batch reaction system for depositing a semiconductor film,the reaction system comprising: a reaction tube configured to hold asubstrate boat to be processed, the reaction tube having a depositedfilm on an interior of the reaction tube, wherein the deposited filmcomprises at least one of: molybdenum or molybdenum nitride; an in situradical generator; a halide precursor source configured to provide ahalide gas to the reaction tube; an inert gas source configured toprovide an inert gas to the reaction tube; an oxygen gas sourceconfigured to provide an oxygen gas to the reaction tube; a firstreactant precursor source configured to provide a first reactantprecursor to the reaction tube; and a second reactant precursor sourceconfigured to provide a second reactant precursor to the reactionchamber; wherein the in situ radical generator is configured to activatethe halide gas to form a radical gas in the reaction tube; and whereinthe radical gas reacts with the deposited film to remove the depositedfilm from the reaction tube.
 20. The batch reaction system of claim 19,wherein the inert gas comprises at least one of: argon; xenon; helium;or nitrogen.
 21. The batch reaction system of claim 19, wherein thehalide gas comprises at least one of: nitrogen trifluoride (NF₃);chlorine trifluoride (ClF₃); fluorine (F₂); chlorine (Cl₂); orcombinations of the above.
 22. The batch reaction system of claim 19,wherein the oxygen gas comprises at least one of: oxygen (O₂); watervapor (H₂O); or hydrogen peroxide (H₂O₂).
 23. The batch reaction systemof claim 19, wherein the first reactant precursor comprises at least oneof: a molybdenum halide precursor; a molybdenum chloride precursor; amolybdenum iodide precursor; a molybdenum bromide precursor; amolybdenum chalcogenide; a molybdenum oxychloride; a molybdenumoxyiodide; a molybdenum (IV) dichloride dioxide (MoO₂Cl₂) precursor; ora molybdenum oxybromide.
 24. The batch reaction system of claim 19,wherein a flow of the halide gas ranges between 10 and 700 sccm, between50 and 500 sccm, or between 100 and 300 sccm.